Propanol and related compounds and their use in perfume compositions

ABSTRACT

The present invention a method of improving, enhancing or modifying a fragrance formulation through the addition of an olfactory acceptable amount of a compound of formula: 
     
       
         
         
             
             
         
       
         
         
           
             wherein R is absent, hydrogen or methyl; 
             R1, R2, and R3 are independently hydrogen or methyl; and 
             the broken lines represent independently single or double bonds, with the proviso that when R1, R2, and R3 are hydrogen, R is methyl.

STATUS OF RELATED APPLICATIONS

This application is a divisional of U.S. Ser. No. 12/269,473, filed Nov.12, 2008, now U.S. Pat. No. 7,691,803, which is hereby incorporated byreference in its entirety.

FIELD OF THE INVENTION

The present invention relates to new chemical entities and theincorporation and use of the new chemical entities as fragrancematerials.

BACKGROUND OF THE INVENTION

There is an ongoing need in the fragrance industry to provide newchemicals to give perfumers and other persons the ability to create newfragrances for perfumes, colognes and personal care products. Those withskill in the art appreciate how differences in the chemical structure ofthe molecule can result in significant differences in the odor, notesand characteristics of a molecule. These variations and the ongoing needto discover and use the new chemicals in the development of newfragrances allow the perfumers to apply the new compounds in creatingnew fragrances.

SUMMARY OF THE INVENTION

The present invention provides novel chemicals, and the use of thechemicals to enhance the fragrance of perfumes, toilet waters, colognes,personal products and the like. In addition, the present invention isdirected to the use of the novel chemicals to enhance fragrance inperfumes, toilet waters, colognes, personal products and the like.

More specifically, the present invention is directed to novel propanoland related compounds and a method of improving, enhancing or modifyinga fragrance formulation through the addition of an olfactory acceptableamount of the novel propanol and related compounds represented byFormula I set forth below:

wherein R is absent, hydrogen or methyl;

R1, R2, and R3 are independently hydrogen or methyl; and

the broken lines represent independently single or double bonds,

with the proviso that when R1, R2, and R3 are hydrogen, R is methyl.

Another embodiment of the invention is directed to a fragranceformulation comprising the propanol and related compounds providedabove.

Another embodiment of the invention is directed to a method forenhancing a perfume composition by incorporating an olfactory acceptableamount of the propanol and related compounds provided above.

These and other embodiments of the present invention will be apparent byreading the following specification.

DETAILED DESCRIPTION OF THE INVENTION

In Formulae I above, R is absent, hydrogen or methyl; R1, R2, and R3 areindependently hydrogen or methyl; and the broken lines at the 2 and 2′positions represent independently single and/or double bonds, with theproviso that when R1, R2, and R3 are all hydrogen, R is methyl.

In one embodiment of the invention, the novel compounds of the inventionare represented by the following structures:

Those with the skill in the art will appreciate that

Formula II is 2-methyl-1-bicyclo[2.2.1]hept-2′-yl-propan-2-ol;

Formula III is2-methyl-1-(5′-methyl-bicyclo[2.2.1]hept-2′-yl)-propan-2-ol;

Formula IV is2-methyl-1-(6′-methyl-bicyclo[2.2.1]hept-2′-yl)-propan-2-ol;

Formula V is1-(5′,6′-dimethyl-bicyclo[2.2.1]hept-2-yl)-2′-methyl-propan-2-ol;

Formula VI is1-(5′,5′-dimethyl-bicyclo[2.2.1]hept-2-yl)-2′-methyl-propan-2-ol;

Formula VII is2-methyl-1-(5′,5′,6′-trimethyl-bicyclo[2.2.1]hept-2′-yl)-propan-2-ol;

Formula VIII is1-(5′,5′,6′-trimethyl-bicyclo[2.2.1]hept-2′-ylidene)-propan-2-one; and

Formula IX is1-(5′,5′,6′-trimethyl-bicyclo[2.2.1]hept-2′-yl)-propan-2-one.

The compounds of the present invention may be prepared withcyclopent-3-enyl-acetaldehydes via a Knoevenagel reaction followed by acyclization reaction. Those with the skill in the art will appreciatethat suitable cyclopent-3-enyl-acetaldehydes include, for example,(cyclopent-3′-enyl)-acetaldehyde,(3′-methyl-cyclopent-3′-enyl)-acetaldehyde,(2′-methyl-cyclopent-3′-enyl)-acetaldehyde,(2′,3′-dimethyl-cyclopent-3′-enyl)-acetaldehyde,(2′,2′-dimethyl-cyclopent-3′-enyl)-acetaldehyde, and(2′,2′,3′-trimethyl-cyclopent-3′-enyl)-acetaldehyde.

The reaction steps can be depicted by a general scheme as follows,wherein the broken lines indicate one double bond located between thecarbon atom at position 3 and the carbon atom at position 2 or 4:

Those with skill in the art will recognize that some of the compounds ofthe present invention have a number of chiral centers, thereby providingnumerous isomers of the claimed compounds. It is intended herein thatthe compounds described herein include isomeric mixtures of suchcompounds, as well as those isomers that may be separated usingtechniques known to those having skill in the art. Suitable techniquesinclude chromatography such as high performance liquid chromatography,referred to as HPLC, and particularly gel chromatography and solid phasemicroextraction, referred to as SPME.

The use of the compounds of the present invention is widely applicablein current perfumery products, including the preparation of perfumes andcolognes, the perfuming of personal care products such as soaps, showergels, and hair care products, fabric care products as well as airfresheners and cosmetic preparations. The present invention can also beused to perfume cleaning agents, such as, but not limited to detergents,dishwashing materials, scrubbing compositions, window cleaners and thelike.

In these preparations, the compounds of the present invention can beused alone or in combination with other perfuming compositions,solvents, adjuvants and the like. The nature and variety of the otheringredients that can also be employed are known to those with skill inthe art.

Many types of fragrances can be employed in the present invention, theonly limitation being the compatibility with the other components beingemployed. Suitable fragrances include but are not limited to fruits suchas almond, apple, cherry, grape, pear, pineapple, orange, strawberry,raspberry; musk, flower scents such as lavender-like, rose-like,iris-like, carnation-like. Other pleasant scents include herbal andwoodland scents derived from pine, spruce and other forest smells.Fragrances may also be derived from various oils, such as essentialoils, or from plant materials such as peppermint, spearmint and thelike.

A list of suitable fragrances is provided in U.S. Pat. No. 4,534,891,the contents of which are incorporated by reference as if set forth inits entirety. Another source of suitable fragrances is found inPerfumes, Cosmetics and Soaps, Second Edition, edited by W. A. Poucher,1959. Among the fragrances provided in this treatise are acacia, cassie,chypre, cyclamen, fern, gardenia, hawthorn, heliotrope, honeysuckle,hyacinth, jasmine, lilac, lily, magnolia, mimosa, narcissus, freshly-cuthay, orange blossom, orchid, reseda, sweet pea, trefle, tuberose,vanilla, violet, wallflower, and the like.

Olfactory effective amount is understood to mean the amount of compoundin perfume compositions the individual component will contribute to itsparticular olfactory characteristics, but the olfactory effect of theperfume composition will be the sum of the effects of each of theperfumes or fragrance ingredients. Thus the compounds of the inventioncan be used to alter the aroma characteristics of the perfumecomposition, or by modifying the olfactory reaction contributed byanother ingredient in the composition. The amount will vary depending onmany factors including other ingredients, their relative amounts and theeffect that is desired.

The level of compounds of the invention employed in the perfumed articlevaries from about 0.005 to about 10 weight percent, preferably fromabout 0.5 to about 8 and most preferably from about 1 to about 7 weightpercent. In addition to the compounds other agents can be used inconjunction with the fragrance. Well known materials such assurfactants, emulsifiers, polymers to encapsulate the fragrance can alsobe employed without departing from the scope of the present invention.

Another method of reporting the level of the compounds of the inventionin the perfumed composition, i.e., the compounds as a weight percentageof the materials added to impart the desired fragrance. The compounds ofthe invention can range widely from 0.005 to about 70 weight percent ofthe perfumed composition, preferably from about 0.1 to about 50 and mostpreferably from about 0.2 to about 25 weight percent. Those with skillin the art will be able to employ the desired level of the compounds ofthe invention to provide the desired fragrance and intensity.

When used in a fragrance formulation this ingredient provides freshnessmaking the fragrance top notes more desirable and noticeable. It alsohas a spicy peppery odor which is very commonly used in men's fragrancesadded for fragrance appropriateness and desirability. The woody part ofit is very useful in both men's and women's fragrances adding body andsubstantivity to the finished product. All of these odor qualities foundin this material assist in beautifying and enhancing the finished accordimproving the performance of the other materials in the fragrance. Thefloral of it will beautify as well and makes the fragrance moredesirable and add the perception of value. There is also the fruity sideof it which is found in many fragrances today which happens to be verytrendy, especially for the younger consumer.

The following are provided as specific embodiments of the presentinvention. Other modifications of this invention will be readilyapparent to those skilled in the art. Such modifications are understoodto be within the scope of this invention. As used herein all percentagesare weight percent unless otherwise noted, ppm is understood to standfor parts per million, L is understood to be liter, mL is understood tobe milliliter, N is understood to be normality, Kg is understood to bekilogram, g is understood to be gram, and mmHg be millimeters (mm) ofmercury (Hg). IFF as used in the examples is understood to meanInternational Flavors & Fragrances Inc., New York, N.Y., USA.

Example I

*the broken lines in the above scheme indicate one double bond locatedbetween the carbon atom at position 3 and the carbon atom at position 2or 4.

Preparation of1-(5′,5′,6′-trimethyl-bicyclo[2.2.1]hept-2′-ylidene)-propan-2-one: Ethylacetoacetate (EAA) (1133 g, commercially available from Sigma-AldrichCorp., St. Louis, Mo.) was added dropwise to a well stirred mixture of(2′,2′,3′-trimethyl-cyclopent-3′-enyl)-acetaldehyde (1204 g,commercially available from Atofina Chemicals NA, Inc., Philadelphia,Pa.), dibutylamine (91 g, commercially available from Sigma-AldrichCorp., St. Louis, Mo.), and acetic acid (AcOH) (43 g, commerciallyavailable from Sigma-Aldrich Corp., St. Louis, Mo.) in 1 L toluene. Thereaction temperature was maintained at about 12-15° C. with an ice-waterbath. The reaction mixture was further stirred for overnight at roomtemperature, and gas chromatographic (GC) analysis indicated thereaction was completed. The reaction mixture was then poured into 1 Naqueous HCl (1 L) and the organic phase was separated and washed with50% brine, saturated aqueous sodium bicarbonate, and water. The lowboiling components, including the solvent of toluene, were removed undera reduced pressure to furnish the mixture of2-acetyl-4-(2′,2′,3′-trimethyl-cyclopent-3′-enyl)-but-2-enoic acid ethylester and 2-acetyl-4-(2′,2′,3′-trimethyl-cyclopent-3′-enyl)-but-3-enoicacid ethyl ester (1913 g). Tin chloride (SnCl₄) (40 mL) was then added.The reaction mixture was stirred for overnight at 80° C. till GCanalysis indicated the reaction was completed. The reaction mixture wasthen poured into 5% aqueous HCl (1 L). The organic phase was separatedand washed with 50% brine and water, to provide3-oxo-2-(5′,5′,6′-trimethyl-bicyclo[2.2.1]hept-2′-ylidene)-butyric acidethyl ester. Water (900 mL) followed by potassium hydroxide (KOH) (840g) were then added in small portions. The mixture was heated at 88° C.for two hours till GC analysis indicated the reaction was completed. Thereaction mixture was poured into 3 N aqueous HCl (1.5 L). The organicphase was separated and washed with 50% brine and water, respectively.The crude product was distilled under a reduced pressure to produce1-(5′,5′,6′-trimethyl-bicyclo[2.2.1]hept-2′-ylidene)-propan-2-one (695g).

Mixture of 2-acetyl-4-(2′,2′,3′-trimethyl-cyclopent-3′-enyl)-but-2-enoicacid ethyl ester and2-acetyl-4-(2′,2′,3′-trimethyl-cyclopent-3′-enyl)-but-3-enoic acid ethylester

¹H NMR: 0.72-1.07 ppm (m), 1.23-1.36 ppm (m), 1.65-1.97 ppm (m),2.12-2.49 ppm (m), 4.08-4.43 ppm (m), 5.23 ppm (s), 5.65-5.97 ppm (m),6.90 ppm (t, J=7.8 Hz), 6.97 ppm (t, J=7.8 Hz)

3-Oxo-2-(5′,5′,6′-trimethyl-bicyclo[2.2.1]hept-2′-ylidene)-butyric acidethyl ester

¹H NMR: 0.90-1.08 ppm (m, 9H), 1.24-1.43 ppm (m, 5H), 1.86-1.94 ppm (m,2H), 2.21-2.33 ppm (m, 3H), 2.34-2.45 ppm (m, 1H), 2.74 ppm (s, 1H),2.79-2.86 ppm (m, 1H), 4.16-4.32 ppm (m, 2H)

1-(5′,5′,6′-Trimethyl-bicyclo[2.2.1]hept-2′-ylidene)-propan-2-one

¹H NMR: 0.91-0.94 ppm (m, ˜90% of 9H), 0.96-1.00 ppm (m, ˜10% of 9H),1.20-1.33 ppm (m, 2H), 1.82-1.90 ppm (m, 2H), 2.16 ppm (s, 3H),2.26-2.45 ppm (m, 2H), 2.94-3.00 ppm (m, ˜79% of 1H), 3.48 ppm (s, ˜21%of 1H), 5.98 ppm (s, ˜24% of 1H), 6.18 ppm (s, ˜76% of 1H)

The product compound1-(5′,5′,6′-trimethyl-bicyclo[2.2.1]hept-2′-ylidene)-propan-2-one wasdescribed as having woody, fruity, fresh, resin, and apple notes.

Example II

Preparation of1-(5′,5′,6′-trimethyl-bicyclo[2.2.1]hept-2′-yl)-propan-2-one: In anautoclave,1-(5′,5′,6′-trimethyl-bicyclo[2.2.1]hept-2′-ylidene)-propan-2-one (490g), 5% palladium (Pd) on carbon (3.6 g), and 2-propanol (100 g) weremixed and stirred at about 70-100° C. for two hours till GC analysisindicated the reaction was completed. The reaction mixture was filteredand distilled under a reduced pressure to produce1-(5′,5′,6′-trimethyl-bicyclo[2.2.1]hept-2′-yl)-propan-2-one (400 g).

¹H NMR: 0.82 ppm (d, 3H, J=7.30 Hz), 0.87 ppm (s, 3H), 0.96 ppm (s, 3H),1.18-1.20 ppm (m, 2H), 1.41-1.47 ppm (m, 1H), 1.62-1.69 ppm (m, 3H),1.82-1.84 ppm (m, 1H), 2.14 ppm (s, 3H), 2.19-2.28 ppm (m, 1H),2.49-2.59 ppm (m, 2H)

The product compound was described as having woody, ionone, and powderynotes.

Example III

Preparation of2-methyl-1-(5′,5′,6′-trimethyl-bicyclo[2.2.1]hept-2′-yl)-propan-2-ol: Asolution of 1-(5′,5′,6′-trimethyl-bicyclo[2.2.1]hept-2′-yl)-propan-2-one(270 g) in 500 mL toluene was added dropwise to a mixture of 3 Nmethylmagnesium chloride (733 mL) and 500 mL toluene at 5° C. Uponcompletion of adding, GC analysis indicated that the reaction wascomplete. The reaction mixture was quenched carefully with 50% aqueousNaOH (200 g), and refluxed for 20 minutes. The liquid was decanted fromthe mixture and the organic phase was separated and washed with 50%brine and water. The crude product was distilled under a reducedpressure to produce2-methyl-1-(5′,5′,6′-trimethyl-bicyclo[2.2.1]hept-2′-yl)-propan-2-ol(172 g).

¹H NMR: 0.82 ppm (d, 3H, J=7.29 Hz), 0.87 ppm (s, 3H), 0.97 ppm (s, 3H),1.14-1.19 ppm (m, 1H), 1.21 ppm (s, 3H), 1.23 ppm (s, 3H), 1.24-1.28 ppm(m, 1H), 1.33-1.38 ppm (m, 1H), 1.43-1.63 ppm (m, 4H), 1.65-1.69 ppm (m,2H), 1.80-1.83 ppm (m, 1H), 1.88-1.93 ppm (m, 1H)

The compound was described as having woody, mossy, tree bark, andpatchouli notes.

Example IV

The fragrance formula exemplified as follows demonstrates that thepropanol compound imparts a woody character to the fragrance formula:

Parts* Ingredients + − AMYL SAL 1.00 1.00 BERGAMOT OIL ITALY MPF“PFG”BLO BHT 10.00 10.00 CLOVE BUD OIL USP 0.20 0.20 COUMARIN 1.00 1.00CYCLACET 3.00 3.00 DIHYDRO MYRCENOL 2.00 2.00 DIPROPYLENE GLYCOL 6.409.40 2-METHYL-1-(5′,5′,6′-TRIMETHYL- 3.00 —BICYCLO[2.2.1]HEPT-2′-YL)-PROPAN-2-OL GALAXOLIDE 50 PCT BB 20.00 20.00HEDIONE BHT 5.00 5.00 HEXENOL, B, GAMMA EXTRA 10% DPG 2.00 2.00 IONONEBETA EXTRA 0.50 0.50 ISO BUTYL QUINOLINE RD“PFG” 1.00 1.00 ISO E SUPERBHT 20.00 20.00 LINALYL ACET 1.00 1.00 LYRAL BHT 7.00 7.00 MANDARIN OILHP“PFG” 7.00 7.00 NUTMEG OIL EI“PFG” 1.00 1.00 ORANGE OIL FLA TYPECP“FLG” 2.50 2.50 TRISAMBER (ELINCS) 10% DPG 1.00 1.00 UNDECAVERTOL MVB1.00 1.00 VERAMOSS 0.40 0.40 VERTOFIX COEUR 4.00 4.00 TOTAL 100.00100.00 *“+” represents a propanol compound containing formula; and “−”represents a propanol compound non-containing formula.

1. A fragrance formulation containing an olfactory effective amount of acompound of formula:

wherein R is absent, hydrogen or methyl; R1, R2, and R3 areindependently hydrogen or methyl; and the broken lines representindependently single or double bonds, with the proviso that when R1, R2,and R3 are hydrogen, R is methyl.
 2. A fragrance product containing anolfactory effective amount of a compound of formula:

wherein R is absent, hydrogen or methyl; R1, R2, and R3 areindependently hydrogen or methyl; and the broken lines representindependently single or double bonds, with the proviso that when R1, R2,and R3 are hydrogen, R is methyl.
 3. A compound of formula:

wherein R is absent, hydrogen or methyl; R1, R2, and R3 areindependently hydrogen or methyl; and the broken lines represent singlebonds, with the proviso that when R1, R2, and R3 are hydrogen, R ismethyl.